全文获取类型
收费全文 | 790篇 |
免费 | 4篇 |
国内免费 | 2篇 |
专业分类
化学 | 613篇 |
晶体学 | 4篇 |
力学 | 16篇 |
数学 | 94篇 |
物理学 | 69篇 |
出版年
2023年 | 3篇 |
2022年 | 12篇 |
2021年 | 5篇 |
2020年 | 5篇 |
2019年 | 6篇 |
2018年 | 4篇 |
2017年 | 6篇 |
2016年 | 6篇 |
2015年 | 7篇 |
2014年 | 10篇 |
2013年 | 30篇 |
2012年 | 48篇 |
2011年 | 67篇 |
2010年 | 39篇 |
2009年 | 27篇 |
2008年 | 70篇 |
2007年 | 57篇 |
2006年 | 57篇 |
2005年 | 56篇 |
2004年 | 41篇 |
2003年 | 42篇 |
2002年 | 21篇 |
2001年 | 10篇 |
1999年 | 5篇 |
1998年 | 6篇 |
1997年 | 14篇 |
1996年 | 11篇 |
1995年 | 7篇 |
1994年 | 7篇 |
1993年 | 6篇 |
1992年 | 10篇 |
1991年 | 3篇 |
1990年 | 4篇 |
1989年 | 2篇 |
1988年 | 5篇 |
1987年 | 5篇 |
1986年 | 3篇 |
1985年 | 9篇 |
1984年 | 10篇 |
1983年 | 8篇 |
1982年 | 6篇 |
1981年 | 5篇 |
1980年 | 5篇 |
1979年 | 10篇 |
1978年 | 4篇 |
1977年 | 3篇 |
1976年 | 5篇 |
1975年 | 6篇 |
1974年 | 2篇 |
1973年 | 2篇 |
排序方式: 共有796条查询结果,搜索用时 15 毫秒
191.
Jean-Luc Fauchre Susanne Pfenninger Kim Quang Do Carole Lemieux Peter W. Schiller 《Helvetica chimica acta》1983,66(4):1053-1060
Converging data obtained in biochemical and pharmacological bioassays for opiate activity are presented for five new enkephalin-like peptides. The main structural features of the analogues, the synthesis of which is described in detail, were the presence of D -alanine or D -serine in position 2, p-nitrophenylalanine in position 4 and of a free C-terminal carboxylic function. Confirming our previous observations [1], the substitution of phenylalanine by p-nitrophenylalanine enhanced the overall opiate activity but decreased the selectivity towards m?/δ-receptor sites. Tyrosyl-D -alanyl-glycyl-p-nitrophenylalanyl-adamantylalanine was particularly potent in all assays while tyrosyl-D -seryl-glycyl-p-nitrophenylalanyl-leucyl-threonine was very selective in the bioassays on isolated tissues and moderately selective in the binding assay. These results will have to be taken into account in future photoaffinity labelling and quantitative structure-activity relationships (QSAR) studies. 相似文献
192.
Johansson BL Belew M Eriksson S Glad G Lind O Maloisel JL Norrman N 《Journal of chromatography. A》2003,1016(1):35-49
Several prototypes of aromatic (Ar) and non-aromatic (NoAr) cation-exchange ligands suitable for capture of proteins from high conductivity (ca. 30 mS/cm) mobile phases were coupled to Sepharose 6 Fast Flow. These new prototypes of multi-modal cation-exchangers were found by screening a diverse library of multi-modal ligands and selecting cation-exchangers resulting in elution of test proteins at high ionic-strength. Candidates were then tested with respect to breakthrough capacity of bovine serum albumin (BSA), human IgG and lysozyme in buffers adjusted to a high conductivity. By applying a salt-step or a pH-step the recoveries were also tested. We have found that aromatic multi-modal cation-exchanger ligands based on carboxylic acids seem to be optimal for the capture of proteins at high-salt conditions. Experimental evidence on the importance of the relative position of the aromatic group in order to improve the breakthrough capacity at high-salt conditions has been found. It was also found that an amide group on the alpha-carbon was essential for capture of proteins at high-salt conditions. Compared to a strong cation-exchanger such as SP Sepharose Fast Flow the best new multi-modal weak cation-exchangers have breakthrough capacities of BSA, human IgG and lysozyme that are 10-30 times higher at high-salt conditions. The new multi-modal cation-exchangers can also be used at normal cation-exchange conditions and with either a salt-step or a pH-step (to pH-values where the proteins are negatively charged) to accomplish elution of proteins. In addition, the functional performance of the new cation-exchangers was found to be intact after treatment in 1.0 M sodium hydroxide solution for 10 days. For BSA it was also possible to design cation-exchangers based on non-aromatic carboxyl acid ligands with high capacities at high-salt conditions. A common feature of these ligands is that they contain hydrogen acceptor groups close to the carboxylic group. Furthermore, it was also possible to obtain high breakthrough capacities for lysozyme and BSA of a strong cation-exchanger (SP Sepharose Fast Flow) if phenyl groups were attached to the beads. Varying the ligand ratio (SP/Phenyl) could be used for optimizing the function of mixed-ligand ion-exchange media. 相似文献
193.
Crispin X Geskin V Crispin A Cornil J Lazzaroni R Salaneck WR Brédas JL 《Journal of the American Chemical Society》2002,124(27):8131-8141
In organics-based (opto)electronic devices, the interface dipoles formed at the organic/metal interfaces play a key role in determining the barrier for charge (hole or electron) injection between the metal electrodes and the active organic layers. The origin of this dipole is rationalized here from the results of a joint experimental and theoretical study based on the interaction between acrylonitrile, a pi-conjugated molecule, and transition metal surfaces (Cu, Ni, and Fe). The adsorption of acrylonitrile on these surfaces is investigated experimentally by photoelectron spectroscopies, while quantum mechanical methods based on density functional theory are used to study the systems theoretically. It appears that the interface dipole formed at an organic/metal interface can be divided into two contributions: (i) the first corresponds to the "chemical" dipole induced by a partial charge transfer between the organic layers and the metal upon chemisorption of the organic molecules on the metal surface, and (ii) the second relates to the change in metal surface dipole because of the modification of the metal electron density tail that is induced by the presence of the adsorbed organic molecules. Our analysis shows that the charge injection barrier in devices can be tuned by modulating various parameters: the chemical potential of the bare metal (given by its work function), the metal surface dipole, and the ionization potential and electron affinity of the organic layer. 相似文献
194.
The l-dimethoxymethyl-5,6-dimethyldene-7-oxabicyclo[2.2.1]hept-2-ene ( 9 ) has been prepared. On treatment with Fe2(CO)9, the endocyclic double bond C(2)?C(3) was coordinated first giving the corresponding exo-Fe(CO)4 complex 10 . The latter reacted with Fe2(CO)9 and afforded cis-heptacarbonyl-μ-[1RS,2SR,3RS,4SR,5RS,6SR-2,3-η: C5,6,C-η-(1-(dimethoxymethyl)-5,6-dimethylidene-7-oxabicyclo[2.2.1]hept-2-ene)]diiron ( 11 ) as a major product. On heating, 11 underwent deoxygenation of the 7-oxabicyclo[2.2.1]heptene moiety yielding tricarbonyl[C,5,6,C-η-(1-(dimethoxymethyl)-5,6-dimethylidenecyclohexa-1,3-diene)]iron ( 13 ). In MeOH, a concurrent, regioselective methoxycarbonylation was observed giving tricarbonyl[C,3,4,C-η-(methyl 5-(dimethoxymethyl)-3,4-dimethylidenecyclohexa-1,5-diene-1-carboxylate)]iron ( 14 ). Oxidative removal of the Fe(CO)3 moiety in 13 and 14 did not afford the expected ortho-quinodimethane derivatives but led to CO insertions giving 2,3-dihydro-2-oxo-1Hindene-4-carbaldehyde ( 20 ) and methyl 7-formyl-2-3-dihydro-2-oxo-lH-indene-5-carboxylate ( 21 ), respectively. 相似文献
195.
The photo-oxidation of [2.2.2]hericene ( 6 ) gave successively the endoperoxides 11 (9,10,11,12-tetramethylidene-4,5-dioxatricyclo[6.2.2.02,7]dodec-2(7)-ene), the bis-endoperoxide 16 (15,16-dimethylidene-4,5,11,12-tetraoxatetracyclo[6.6.2.02,7.o9,14]hexadeca-2(7),9(14)-diene), and the tris-endoperoxide 19 (4,5,11,12,17,18-hexaoxapentacyclo[6.6.6.02,7.09,14.015,20]icosa-2(7),9(14),15(20)-triene). The endoperoxides 11, 16 , and 19 were formed in the presence or in the absence of a dye sensitizer. The sensitized photo-oxidations of 2,3,5,6-tetramethylidenebicyclo[2.2.2]octane ( 4 ), 5,6,7,8-tetramethylidenebicyclo[2.2.2]oct-2-ene ( 5 ), 2,3,5,6-tetramethylidenebicyclo[2.2.1]-heptane ( 7 ), and 2,3,5,6-tetramethylidene-7-oxabicyclo[2.2.1]heptane ( 8 ) gave successively the corresponding mono-endoperoxides 9, 10, 12 , and 13 and the bis-endoperoxides 14, 15, 17 , and 18 , respectively. Low-temperature NMR spectra of the bis-endoperoxides 14 and 16 indicated that their C2 and Cs conformers have the same stability. Similarly, there was no difference in the enthalpy of the D3 and C2 conformers of the tris-endoperoxide 19 . The following reactivity sequence was observed for the sensitized photo-oxidations of 6–8 and 5,6-dimethylidene-7-oxabicyclo[2.2.1]hept-2-ene ( 23 ): 6 + 1O2→ 11 > 7 + 1O2→ 12 > 8 + 1O2→ 13 > 23 + 1O2→ 24 , a trend parallel with that reported for the ethylenetetracarbonitrile (TCNE) cycloadditions to the same polyenes. The rate-constant ratios k1/k2 and k2/k3 for the three successive photo-oxidations of [2.2.2]hericene ( 6 ) did not differ significantly from unity, in contrast with the Diels-Alder additions of 6 . Similarly, the rate-constant ratios k1/k2 for the two successive photo-oxidations of tetraenes 7 and 8 were significantly smaller than those reported for the successive TCNE cycloadditions to 7 to 8 . The endoperoxide formations are not sensitive to the change in the exothermicity of the reactions but they are sensitive to the electronic properties (IP's) of the polyenes. 相似文献
196.
Raymond Houssin Jean-Luc Bernier Jean-Pierre Hnichart 《Journal of heterocyclic chemistry》1985,22(5):1185-1187
An unequivocal synthesis of a new thiazolo[2,3-c]-s-triazole substituted at the C-5 position by a very useful methyl triphenylphosphonium salt has been achieved starting from the corresponding 2-isopropylidenehydrazinylthiazole and formic acid. Ring closure was found to be very easy without isolation of a formylhydrazino intermediate. The thiazole derivative was prepared from isopropylidenethiosemicarbazide and (3-chloro-2-oxo)propyltriphenylphosphonium chloride in a good yield. 相似文献
197.
By using neutron diffraction together with anomalous dispersion X-ray diffraction, it has been possible to ascertain the distribution of close atomic numbered cations in CoMnxFe2?xO4 system spinels.At 950°C, these compounds have a cubic structure in the range 0 ? x ? 1.25 and exhibit a macroscopic tetragonal distortion as soon as 60% of the Mn3+ ions occupy octahedral sites.The great mobility of cobalt between both types of sites has been pointed out; it can be related to oxidation and reduction phenomena. In these compounds, Fe3+ iron remains neutral towards four or six coordinences. 相似文献
198.
Barlow S Risko C Coropceanu V Tucker NM Jones SC Levi Z Khrustalev VN Antipin MY Kinnibrugh TL Timofeeva T Marder SR Brédas JL 《Chemical communications (Cambridge, England)》2005,(6):764-766
The E-4,4'-bis[di(p-anisyl)amino]stilbene cation is a class-III mixed-valence species with electronic coupling comparable to that in its biphenyl-bridged analogue, whereas its tolane-bridged analogue belongs to class II. 相似文献
199.
Aggarwal VK Alonso E Bae I Hynd G Lydon KM Palmer MJ Patel M Porcelloni M Richardson J Stenson RA Studley JR Vasse JL Winn CL 《Journal of the American Chemical Society》2003,125(36):10926-10940
A variety of metalated tosylhydrazone salts derived from benzaldehyde have been prepared and were reacted with benzaldehyde in the presence of tetrahydrothiophene (THT) (20 mol %) and Rh(2)(OAc)(4) (1 mol %) to give stilbene oxide. Of the lithium, sodium, and potassium salts tested, the sodium salt was found to give the highest yield and selectivity. This study was extended to a wide variety of aromatic, heteroaromatic, aliphatic, alpha,beta-unsaturated, and acetylenic aldehydes and to ketones. On the whole, high yields of epoxides with moderate to very high diastereoselectivities were observed. A broad range of tosylhydrazone salts derived from aromatic, heteroaromatic, and alpha,beta-unsaturated aldehydes was also examined using the same protocol in reactions with benzaldehyde, and again, good yields and high diastereoselectivities were observed in most cases. Thus, a general process for the in situ generation of diazo compounds from tosylhydrazone sodium salts has been established and applied in sulfur-ylide mediated epoxidation reactions. The chiral, camphor-derived, [2.2.1] bicyclic sulfide 7 was employed (at 5-20 mol % loading) to render the above processes asymmetric with a range of carbonyl compounds and tosylhydrazone sodium salts. Benzaldehyde tosylhydrazone sodium salt gave enantioselectivities of 91 +/- 3% ee and high levels of diastereoselectivity with a range of aldehydes. However, tosylhydrazone salts derived from a range of carbonyl compounds gave more variable selectivities. Although those salts derived from electron-rich or neutral aldehydes gave high enantioselectivities, those derived from electron-deficient or hindered aromatic aldehydes gave somewhat reduced enantioselectivities. Using alpha,beta-unsaturated hydrazones, chiral sulfide 7 gave epoxides with high diastereoselectivities, but only moderate yields were achieved (12-56%) with varying degrees of enantioselectivity. A study of solvent effects showed that, while the impact on enantioselectivity was small, the efficiency of diazo compound generation was influenced, and CH(3)CN and 1,4-dioxane emerged as the optimum solvents. A general rationalization of the factors that influence both relative and absolute stereochemistry for all of the different substrates is provided. Reversibility in formation of the betaine intermediate is an important issue in the control of diastereoselectivity. Hence, where low diastereocontrol was observed, the results have been rationalized in terms of the factors that contribute to the reduced reversion of the syn betaine back to the original starting materials. The enantioselectivity is governed by ylide conformation, facial selectivity in the ylide reaction, and, again, the degree of reversibility in betaine formation. From experimental evidence and calculations, it has been shown that sulfide 7 gives almost complete control of facial selectivity, and, hence, it is the ylide conformation and degree of reversibility that are responsible for the enantioselectivity observed. A simple test has been developed to ascertain whether the reduced enantioselectivity observed in particular cases is due to poor control in ylide conformation or due to partial reversibility in the formation of the betaine. 相似文献
200.
Jean-Luc Fortier Patrick R. Philip Jacques E. Desnoyers 《Journal of solution chemistry》1974,3(7):523-538
The volumetric specific heats and densities of alkali fluorides, alkali bromides, and soduum halides were measured in D2O at 25°C in the concentration range 0.05 to 1 aquamolal. The results can be combined with data in H2O to give the corresponding standard and excess transfer functions from H2O to D2O. The volumes and heat capacities of transfer are both negative but, contrary to the hydration functions, show little dependence on ionic size and sign. Also, while heats, entropies, and volumes of transfer are usually small compared with the hydration functions, the heat capacity of transfer is of comparable magnitude. These observations, when interpreted with the Frank and Wen model, suggest that the total number of water molecules in the hydration cosphere is approximately constant for all alkali halides and that heat capacities are more sensitive to structural interactions than volumes and enthalpies. The sign of the excess transfer functions is consistent with the presence of structural ion-ion interactions, but no systematic trend with ionic size can be detected in view of the large experimental uncertainty. 相似文献